JP4344399B1 - Curable inorganic composition - Google Patents

Curable inorganic composition Download PDF

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JP4344399B1
JP4344399B1 JP2009013878A JP2009013878A JP4344399B1 JP 4344399 B1 JP4344399 B1 JP 4344399B1 JP 2009013878 A JP2009013878 A JP 2009013878A JP 2009013878 A JP2009013878 A JP 2009013878A JP 4344399 B1 JP4344399 B1 JP 4344399B1
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inorganic composition
curable inorganic
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oxide
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JP2010168503A (en
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哲次 竹澤
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TRIO CERAMICS CO., LTD.
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Priority to KR20117019685A priority patent/KR101162347B1/en
Priority to PCT/JP2009/007183 priority patent/WO2010084555A1/en
Priority to CN200980158224.2A priority patent/CN102361819B/en
Priority to TW99100282A priority patent/TW201038504A/en
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Abstract

【課題】耐熱性および耐火性を有する接着剤、塗料、コーティング剤または充填剤等として、良好な施工性且つ低コストで使用可能な硬化性無機組成物を提供する。
【解決手段】本発明に係る硬化性無機組成物は、水ガラスを１００重量部に対し、フライアッシュを２５〜３５重量部と、金属酸化物と、を予め混合してなる。
【選択図】図１Disclosed is a curable inorganic composition that can be used with good workability and low cost as an adhesive, paint, coating agent or filler having heat resistance and fire resistance.
The curable inorganic composition according to the present invention is prepared by previously mixing 25 to 35 parts by weight of fly ash with 100 parts by weight of water glass and a metal oxide.
[Selection] Figure 1

Description

本発明は、接着剤、塗料、コーティング剤または充填剤等として使用される硬化性無機組成物に関し、特に耐熱性および耐火性を有するものに関する。   The present invention relates to a curable inorganic composition used as an adhesive, a paint, a coating agent, a filler or the like, and particularly relates to one having heat resistance and fire resistance.

従来、例えば合板や壁紙等の建材に使用される接着剤は有機系のものがほとんどであった。この有機系接着剤は、乾燥性や塗布性といった施工性が良好である反面、耐熱性に劣るという欠点があった。近年では、防災意識の高まりと共に建築基準法が改正される等、建材や建物の構造等に対して従来以上に耐熱性、耐火性が要求されるようになっている。このため、建築の分野において使用される接着剤についても従来以上に耐熱性に優れるものが求められているが、有機系接着剤では耐熱性の向上に限界があり、その要求を十分に満たせるものはなかった。   Conventionally, most adhesives used for building materials such as plywood and wallpaper have been organic. While this organic adhesive has good workability such as drying and coating properties, it has a drawback of poor heat resistance. In recent years, the building standards law has been revised with increasing awareness of disaster prevention, and more heat resistance and fire resistance are required than ever for building materials and building structures. For this reason, adhesives used in the field of construction are also required to have better heat resistance than conventional adhesives, but organic adhesives have limitations in improving heat resistance and can sufficiently satisfy the requirements. There was no.

一方、優れた耐熱性、耐火性を有する接着剤として、無機系の接着剤が従来知られている。この無機系の接着剤としては、一般に、水ガラスやコロイダルシリカをバインダとし、アルミナ等の酸化物をフィラーとして混合したものが知られている。このうち、水ガラスを用いた無機系接着剤は、水ガラスが空気中の炭酸ガスを吸収してゲル状ケイ酸が析出してガラス状となり、強い接着力を発揮するため、ガラスや陶磁器等の接着剤や耐火コーティング剤等に用いられている。また、水ガラスを用いた無機系接着剤は一般に硬化速度が遅いため、五酸化アンチモンを加えることにより、硬化速度を高める提案等もされている（例えば特許文献１参照）。   On the other hand, inorganic adhesives are conventionally known as adhesives having excellent heat resistance and fire resistance. As this inorganic adhesive, generally, a mixture of water glass or colloidal silica as a binder and an oxide such as alumina as a filler is known. Of these, inorganic adhesives that use water glass absorb water carbon dioxide in the air and gel silicic acid precipitates to form a glass that exhibits strong adhesive strength, such as glass and ceramics. It is used for adhesives and fireproof coatings. In addition, since inorganic adhesives using water glass generally have a low curing rate, proposals have been made to increase the curing rate by adding antimony pentoxide (see, for example, Patent Document 1).

特開平６−２５６１０号公報JP-A-6-25610

しかしながら、従来の無機系接着剤は、アルミナ等の酸化物を使用することから有機系接着剤よりもはるかに高コストになるという問題があった。このため、接着剤を大量に使用する建築の分野、例えば合板の製造や壁紙の貼付等には、採算面から使用できるものではなかった。また、従来の無機系接着剤は、硬化速度が遅いことから施工性が悪く、風雨に曝されることの多い建築現場での使用に耐えうるものではなかった。従って、従来の無機系接着剤は、優れた耐熱性、耐火性を備えながらも、建築の分野において接着剤またはコーティング剤等に使用されることはまれであった。   However, the conventional inorganic adhesive has a problem that it is much more expensive than the organic adhesive because it uses an oxide such as alumina. For this reason, it cannot be used from the profit side in the field of architecture in which a large amount of adhesive is used, for example, the manufacture of plywood and the application of wallpaper. In addition, conventional inorganic adhesives have poor workability due to their slow curing speed, and have not been able to withstand use at construction sites that are often exposed to wind and rain. Therefore, the conventional inorganic adhesives are rarely used as adhesives or coating agents in the field of construction while having excellent heat resistance and fire resistance.

また、特許文献１に記載の無機系接着剤は、硬化速度（乾燥速度）を高めて施工性を向上させているが、水ガラスと五酸化アンチモンの反応助剤としてアルコールを使用すると共に攪拌中の温度管理が必要である等、製造工程が複雑であるため、従来以上に高コストのものとなっていた。従って、大量に使用される建築の分野において使用できるものではなかった。   In addition, the inorganic adhesive described in Patent Document 1 improves the workability by increasing the curing rate (drying rate), but using alcohol as a reaction aid for water glass and antimony pentoxide and stirring. Since the manufacturing process is complicated, such as the need for temperature control, it has become more expensive than before. Therefore, it could not be used in the field of architecture used in large quantities.

本発明は、このような問題点に鑑みてなされたものであって、耐熱性および耐火性を有する接着剤、塗料、コーティング剤または充填剤等として、良好な施工性且つ低コストで使用可能な硬化性無機組成物を提供しようとするものである。   The present invention has been made in view of such problems, and can be used as a heat-resistant and fire-resistant adhesive, paint, coating agent, filler or the like with good workability and low cost. It is an object to provide a curable inorganic composition.

（１）本発明は、水ガラスを１００重量部に対し、フライアッシュを２５〜３５重量部と、金属酸化物と、を予め混合してなることを特徴とする、硬化性無機組成物である。   (1) The present invention is a curable inorganic composition obtained by previously mixing 25 to 35 parts by weight of fly ash and a metal oxide with respect to 100 parts by weight of water glass. .

（２）本発明はまた、前記金属酸化物として酸化亜鉛を、水ガラス１００重量部に対して１５〜２５重量部を予め混合し、さらにジルコンフラワーを、水ガラス１００重量部に対して５〜１５重量部を予め混合してなることを特徴とする、上記（１）に記載の硬化性無機組成物である。   (2) In the present invention, zinc oxide as the metal oxide is mixed in advance in an amount of 15 to 25 parts by weight with respect to 100 parts by weight of water glass, and zircon flour is further added in an amount of 5 to 100 parts by weight of water glass. The curable inorganic composition as described in (1) above, wherein 15 parts by weight are mixed in advance.

（３）本発明はまた、少なくとも前記水ガラスと、前記フライアッシュと、前記酸化亜鉛と、前記ジルコンフラワーと、を混合した結果、二酸化ケイ素を２２〜４０重量％と、酸化亜鉛を１０〜１５重量％と、酸化ナトリウムを３〜１５重量％と、酸化アルミニウムを３〜１０重量％と、酸化ジルコニウムを２〜８重量％と、水と、を含むことを特徴とする、上記（２）に記載の硬化性無機組成物である。


(3) In the present invention, as a result of mixing at least the water glass, the fly ash, the zinc oxide, and the zircon flour, 22 to 40% by weight of silicon dioxide and 10 to 15 of zinc oxide are obtained. (2) above, characterized by comprising, by weight, 3 to 15% by weight of sodium oxide, 3 to 10% by weight of aluminum oxide, 2 to 8% by weight of zirconium oxide, and water. It is a curable inorganic composition of description.


（４）本発明はまた、前記フライアッシュ、前記金属酸化物、および前記ジルコンフラワーは、それぞれ４５μｍ以下の粒子径のものが含まれることを特徴とする、上記（２）または（３）に記載の硬化性無機組成物である。   (4) In the present invention, the fly ash, the metal oxide, and the zircon flower each include particles having a particle size of 45 μm or less, as described in (2) or (3) above It is a curable inorganic composition.

本発明に係る硬化性無機組成物によれば、耐熱性および耐火性を有する接着剤、塗料、コーティング剤または充填剤等として、良好な施工性且つ低コストで使用可能という優れた効果を奏し得る。   According to the curable inorganic composition according to the present invention, an excellent effect that it can be used with good workability and low cost as an adhesive, paint, coating agent or filler having heat resistance and fire resistance can be obtained. .

接着強度試験の結果を示した図である。It is the figure which showed the result of the adhesive strength test.

本実施形態の硬化性無機組成物に使用する水ガラスは、ケイ酸ナトリウムの濃水溶液であり、ケイ酸ナトリウムを水に溶かし、加熱することによって得られる。水ガラスの組成は、Ｎａ２Ｏ・ｎＳｉＯ２であり、水ガラス中にはＮａ２Ｏ（酸化ナトリウム）およびＳｉＯ２（二酸化ケイ素、シリカ）が混合して存在している。この水ガラスは、市販のものを使用することができるが、モル比ｎの値が小さい場合は製造した組成物が硬化しにくいものとなり、モル比ｎの値が大きい場合は製造した組成物の保管時の安定性が悪化することとなる。従って、水ガラスは、硬化性無機組成物の硬化速度と安定性のバランスの点から、例えばＪＩＳ Ｋ１４０８の１号（Ｎａ２Ｏが１７〜１９重量％、ＳｉＯ２が３５〜３８重量％）または２号（Ｎａ２Ｏが１４〜１５重量％、ＳｉＯ２が３４〜３６重量％）に規定されるものが好ましく、さらにモル比ｎの値が２〜２．３のものであればより好ましい。 The water glass used for the curable inorganic composition of this embodiment is a concentrated aqueous solution of sodium silicate, and is obtained by dissolving sodium silicate in water and heating. The composition of the water glass is Na 2 O · nSiO 2 , and Na 2 O (sodium oxide) and SiO 2 (silicon dioxide, silica) are mixed and present in the water glass. As this water glass, a commercially available product can be used. However, when the molar ratio n is small, the produced composition is difficult to cure, and when the molar ratio n is large, the produced composition is The stability at the time of storage will deteriorate. Accordingly, water glass is, for example, JIS K1408 No. 1 (Na 2 O: 17 to 19% by weight, SiO 2: 35 to 38% by weight) or from the point of balance between the curing speed and stability of the curable inorganic composition or No. 2 (Na 2 O is 14 to 15 wt%, SiO 2 is 34 to 36 wt%) is preferable, and the molar ratio n is more preferably 2 to 2.3.

フライアッシュは、例えば石炭火力発電所の微粉炭燃焼ボイラの燃焼ガスから集塵機で採取された石炭灰である。微粉炭燃焼ボイラにおいて微粉炭を燃焼させた際に生じる灰の粒子は、溶融状態で高温の燃焼ガス中を浮遊した後にボイラ出口で冷却されることにより、球形の微細粒子となる。この球形の微細粒子がフライアッシュであり、その組成は、例えばＳｉＯ２（二酸化ケイ素、シリカ）が４０．１〜７４．４重量％、Ａｌ２Ｏ３（酸化アルミニウム、アルミナ）が１５．７〜３５．２重量％、Ｆｅ２Ｏ３（酸化鉄）が１．４〜１７．５重量％、ＭｇＯ（酸化マグネシウム）が０．２〜７．４重量％、ＣａＯ（酸化カルシウム）が０．３〜１０．１重量％となっている。 Fly ash is, for example, coal ash collected with a dust collector from the combustion gas of a pulverized coal combustion boiler of a coal-fired power plant. Ash particles produced when pulverized coal is burned in a pulverized coal combustion boiler floats in a high-temperature combustion gas in a molten state, and then cools at the boiler outlet to become spherical fine particles. These spherical fine particles are fly ash, and the composition thereof is, for example, 40.1 to 74.4% by weight of SiO 2 (silicon dioxide, silica), and 15.7 to 4% of Al 2 O 3 (aluminum oxide, alumina). 35.2 wt%, Fe 2 O 3 (iron oxide) is from 1.4 to 17.5 wt%, MgO (magnesium oxide) is from 0.2 to 7.4 wt%, CaO (calcium oxide) is 0.3 It is ˜10.1% by weight.

フライアッシュは、ボイラ等の内部における高温燃焼により生じた灰であり、可燃成分がほとんど残存していないため、混和することで硬化性無機組成物の耐熱製、耐火性を向上させることができる。さらに、フライアッシュは球形の微粒子であるため、混和することで硬化性無機組成物の流動性を高めることができる。従って、本実施形態の硬化性無機組成物では、フライアッシュを使用することにより、製造時の攪拌性を向上させると共に、施工時の塗布性や充填性を向上させるようにしている。   Fly ash is ash generated by high-temperature combustion in a boiler or the like, and almost no flammable component remains, so mixing it can improve the heat resistance and fire resistance of the curable inorganic composition. Furthermore, since fly ash is a spherical fine particle, the fluidity | liquidity of a curable inorganic composition can be improved by mix | blending. Therefore, in the curable inorganic composition of this embodiment, by using fly ash, the stirrability at the time of manufacture is improved, and the applicability and filling property at the time of construction are improved.

なお、従来、コンクリートにフライアッシュを混和することにより、ＣａＯと水が反応して生成されたＣａ（ＯＨ）２（水酸化カルシウム）とＳｉＯ２またはＡｌ２Ｏ３が常温でゆっくりと反応するポゾラン反応が生じ、長期強度が向上することが知られている。また、コンクリートにフライアッシュを混和した場合、コンクリートの骨材中の準安定なＳｉＯ２とアルカリイオン・水酸基イオンが反応するアルカリシリカ反応が抑制されることが知られている。 Conventionally, by mixing fly ash with concrete, Ca (OH) 2 (calcium hydroxide) produced by the reaction of CaO with water and SiO 2 or Al 2 O 3 react slowly at room temperature. It is known that reaction occurs and long-term strength is improved. In addition, it is known that when fly ash is mixed with concrete, alkali silica reaction in which metastable SiO 2 in the aggregate of the concrete reacts with alkali ions / hydroxyl ions is suppressed.

本実施形態の硬化性無機組成物では、このようなフライアッシュの特性を利用することで硬化速度と保管時の安定性のバランスをとり、硬化速度を高めながらも保管時の安定性を維持することを可能としている。また、硬化後の無機組成物の長期的な強度および接着力を高めることを可能としている。   In the curable inorganic composition of the present embodiment, by utilizing such fly ash characteristics, the curing speed and storage stability are balanced, and the storage stability is maintained while increasing the curing speed. Making it possible. Further, it is possible to increase the long-term strength and adhesive strength of the cured inorganic composition.

フライアッシュは、石炭火力発電所の副産物として大量に生産されるため、シリカやアルミナよりもはるかに安価に購入することが可能であり、市販のものを使用することができる。フライアッシュを組成物内に十分に混和させて硬化性無機組成物の均質性を向上させ、無機組成物の性能を安定して発揮させるためには、フライアッシュは粒子径が４５μｍ以下（例えば１〜４５μｍ）のものであることが望ましく、粒子径が３０μｍ以下（例えば１〜３０μｍ）であればより望ましい。   Since fly ash is produced in large quantities as a by-product of a coal-fired power plant, it can be purchased at a much lower price than silica and alumina, and commercially available products can be used. In order to improve the homogeneity of the curable inorganic composition by sufficiently mixing the fly ash in the composition and to stably exhibit the performance of the inorganic composition, the fly ash has a particle size of 45 μm or less (for example, 1 ˜45 μm), and more preferably 30 μm or less (for example, 1 to 30 μm).

粒子径が４５μｍ以下または３０μｍ以下のフライアッシュは、例えば４５μｍふるいまたは３０μｍふるいを使用して得ることができる。なお、フライアッシュの粒子径は、全てが４５μｍ（３０μｍ）以下である必要はなく、４５μｍ（３０μｍ）以上のものが一部含まれていてもよいことは言うまでもない。   Fly ash having a particle size of 45 μm or less or 30 μm or less can be obtained using, for example, a 45 μm sieve or a 30 μm sieve. It is needless to say that all the fly ash particle diameters are not necessarily 45 μm (30 μm) or less, and some of them may be 45 μm (30 μm) or more.

従って、コスト面および入手のしやすさ等を考慮した場合、フライアッシュは、例えばＪＩＳ Ａ６２０１のＩＩ種（ＳｉＯ２の割合が４５％以上であり、４５μｍふるい残分が４０％以下、且つブレーン法による比表面積が２５００ｃｍ２／ｇ以上）またはＩ種（ＳｉＯ２の割合が４５％以上であり、４５μｍふるい残分が１０％以下、且つブレーン法による比表面積が５０００ｃｍ２／ｇ以上）に規定されるものが好ましい。 Accordingly, in consideration of cost and availability, fly ash is, for example, JIS A6201 type II (the proportion of SiO 2 is 45% or more, the 45 μm sieve residue is 40% or less, and the brain method Specific surface area by 2500 cm 2 / g or more) or type I (SiO 2 ratio is 45% or more, 45 μm sieve residue is 10% or less, and specific surface area by the brain method is 5000 cm 2 / g or more). Those are preferred.

金属酸化物は、本実施形態の硬化性無機組成物では、酸化亜鉛（ＺｎＯ）を使用している。この酸化亜鉛は、微粉末状の酸化物であり、塗料の塗膜強化剤等として一般に使用されているものである。本実施形態では、酸化亜鉛を適宜に混入することにより、硬化性無機組成物の粘度を調節し、施工時の塗布性や粘着性を向上させている。酸化亜鉛は、市販のものを使用することができるが、十分に混和させて組成物内に均質に分散させるためには、粒子径が４５μｍ以下（例えば１〜４５μｍ）のものが好ましく、粒子径が３０μｍ以下（例えば１〜３０μｍ）のものであればより好ましい。   As the metal oxide, zinc oxide (ZnO) is used in the curable inorganic composition of the present embodiment. This zinc oxide is an oxide in the form of a fine powder and is generally used as a coating film strengthening agent for paints. In this embodiment, the viscosity of a curable inorganic composition is adjusted by mixing zinc oxide appropriately, and the applicability | paintability at the time of construction and adhesiveness are improved. A commercially available zinc oxide can be used, but in order to mix thoroughly and disperse uniformly in the composition, those having a particle size of 45 μm or less (for example, 1 to 45 μm) are preferable. Is more preferably 30 μm or less (for example, 1 to 30 μm).

粒子径が４５μｍ（３０μｍ）以下の金属酸化物は、例えばふるいを使用して得ることができ、４５μｍ（３０μｍ）以上のものが一部含まれていてもよいことは、上述のフライアッシュと同様である。   The metal oxide having a particle diameter of 45 μm (30 μm) or less can be obtained by using, for example, a sieve, and a part of 45 μm (30 μm) or more may be included as in the above fly ash. It is.

なお、金属酸化物は、上述の酸化亜鉛に限定されるものではなく、例えばマグネシウム、カルシウム、鉄、ホウ素等、他の金属の酸化物を使用することができる。また、１種類の金属酸化物のみを使用してもよいし、複数種類の金属酸化物を使用してもよい。   In addition, a metal oxide is not limited to the above-mentioned zinc oxide, For example, oxides of other metals, such as magnesium, calcium, iron, boron, can be used. Moreover, only one type of metal oxide may be used, or a plurality of types of metal oxides may be used.

本実施形態の硬化性無機組成物では、上述の成分に加え、さらにジルコンフラワーを混入している。このジルコンフラワーは、ジルコンサンドを機械的に粉砕分球生成した粉末ジルコン（ケイ酸ジルコニウム、ＺｒＳｉＯ４）である。ジルコンフラワーは溶融点が高く熱膨張が少ないため、硬化性無機組成物の耐熱性および耐火性の向上に貢献する。さらに、ジルコンフラワーは非水溶性であるため、硬化性無機組成物の耐水性の向上に貢献する。 In the curable inorganic composition of the present embodiment, zircon flour is further mixed in addition to the above components. This zircon flour is powdered zircon (zirconium silicate, ZrSiO 4 ) obtained by mechanically pulverizing and dividing zircon sand. Since zircon flour has a high melting point and low thermal expansion, it contributes to improving the heat resistance and fire resistance of the curable inorganic composition. Furthermore, since zircon flour is insoluble in water, it contributes to improving the water resistance of the curable inorganic composition.

また、ジルコンフラワーは、混入されたガラスのガラス軟化点を下げる効果を有しているため、硬化性無機組成物が加熱されてガラス化した場合の柔軟性を増し、脆化を防ぐことができる。これにより、例えば硬化性無機組成物を耐火コーティングとして使用した場合に、加熱時の塗膜の保持性を高め、容易に剥がれ落ちないようにすることができる。   In addition, since zircon flour has an effect of lowering the glass softening point of mixed glass, it can increase flexibility and prevent embrittlement when the curable inorganic composition is heated to vitrify. . Thereby, for example, when a curable inorganic composition is used as a fireproof coating, it is possible to improve the retention of the coating film during heating and prevent it from peeling off easily.

ジルコンフラワーは、シリカやアルミナよりも比較的安価に購入することが可能であり、市販のものを使用することができるが、十分に混和させて組成物内に均質に分散させるためには、粒子径が４５μｍ以下（例えば１〜４５μｍ）のものが好ましく、さらに、粒子径が３０μｍ以下（例えば１〜３０μｍ）であればより好ましい。   Zircon flour can be purchased relatively cheaply than silica and alumina, and commercially available ones can be used, but in order to mix well and disperse homogeneously in the composition, particles A diameter of 45 μm or less (for example, 1 to 45 μm) is preferable, and a particle diameter of 30 μm or less (for example, 1 to 30 μm) is more preferable.

粒子径が４５μｍ（３０μｍ）以下のジルコンフラワーは、例えばふるいを使用して得ることができ、４５μｍ（３０μｍ）以上のものが一部含まれていてもよいことは、上述のフライアッシュおよび金属酸化物と同様である。   Zircon flour having a particle size of 45 μm (30 μm) or less can be obtained using, for example, a sieve, and some of those having a particle size of 45 μm (30 μm) or more may be contained. It is the same as a thing.

本実施形態の硬化性無機組成物の製造は、水ガラスを１００重量部に対し、フライアッシュを２５〜３５重量部と、酸化亜鉛を１５〜２５重量部と、ジルコンフラワーを５〜１５重量部と、を容器内で攪拌して混合することによって行われる。   Production of the curable inorganic composition of this embodiment is based on 100 parts by weight of water glass, 25 to 35 parts by weight of fly ash, 15 to 25 parts by weight of zinc oxide, and 5 to 15 parts by weight of zircon flour. Are mixed by stirring in a container.

水ガラス１００重量部に対するフライアッシュの割合は、硬化性無機組成物の硬化速度と安定性のバランスの点から２５〜３５重量部であることが好ましい。フライアッシュの割合が２５重量部未満の場合は硬化速度が低下し、３５重量部より大きい場合は保管時の安定性が悪化して長期保存が困難となるため好ましくない。   The ratio of fly ash to 100 parts by weight of water glass is preferably 25 to 35 parts by weight from the viewpoint of the balance between the curing speed and stability of the curable inorganic composition. When the fly ash ratio is less than 25 parts by weight, the curing rate decreases, and when it exceeds 35 parts by weight, stability during storage deteriorates and long-term storage becomes difficult, which is not preferable.

水ガラス１００重量部に対する金属酸化物の割合は、特に限定されるものではなく、硬化性無機組成物の用途に応じた粘度となるように、適宜に割合を決定することができる。また、使用する金属酸化物の種類に応じて適宜に割合を決定することができる。   The ratio of the metal oxide with respect to 100 parts by weight of water glass is not particularly limited, and the ratio can be appropriately determined so as to have a viscosity according to the use of the curable inorganic composition. Further, the ratio can be appropriately determined according to the type of metal oxide to be used.

なお、金属酸化物として酸化亜鉛を使用した場合の割合は、水ガラス１００重量部に対して１５〜２５重量部であることが、良好な施工性を得られる適切な粘度となる点から好ましい。但し、酸化亜鉛の割合は、硬化性無機組成物の用途に応じて変更してもよい。例えば、硬化性無機組成物をパテや充填剤として使用する場合は、酸化亜鉛を水ガラス１００重量部に対して２５重量部以上加えるようにしてもよい。   In addition, it is preferable that the ratio at the time of using a zinc oxide as a metal oxide is 15-25 weight part with respect to 100 weight part of water glass from the point used as the suitable viscosity from which favorable workability is obtained. However, you may change the ratio of a zinc oxide according to the use of a curable inorganic composition. For example, when using a curable inorganic composition as a putty or a filler, 25 parts by weight or more of zinc oxide may be added to 100 parts by weight of water glass.

水ガラス１００重量部に対するジルコンフラワーの割合は、特に限定されるものではないが、適切な耐火性を得ると共に適切なガラス軟化点を設定する点から、５〜１５重量部であることが好ましい。   The ratio of zircon flour to 100 parts by weight of water glass is not particularly limited, but it is preferably 5 to 15 parts by weight from the viewpoint of obtaining appropriate fire resistance and setting an appropriate glass softening point.

なお、硬化性無機組成物の粘度を調節するために、少量の水（例えば１〜１５重量％程度）を加えるようにしてもよい。   In order to adjust the viscosity of the curable inorganic composition, a small amount of water (for example, about 1 to 15% by weight) may be added.

混合方法は、公知の方法を用いることができる。また、混合は室温で行うことができる。さらに、各成分を十分に混合した後に密閉容器内で冷暗所に１日程度放置することにより、組成物の性状が安定し、所定の粘性と光沢が表れる。   A known method can be used as the mixing method. Mixing can be performed at room temperature. Furthermore, by thoroughly mixing the components and leaving them in a cool and dark place for about 1 day in a sealed container, the properties of the composition are stabilized, and predetermined viscosity and gloss appear.

得られた硬化性無機組成物は、成分として二酸化ケイ素（ＳｉＯ２）を２２〜４０重量％と、酸化亜鉛（ＺｎＯ）を１０〜１５重量％と、酸化ナトリウム（Ｎａ２Ｏ）を３〜１５重量％と、酸化アルミニウム（Ａｌ２Ｏ３）を３〜１０重量％と、酸化ジルコニウム（ＺｒＯ２）を２〜８重量％と、水と、を含んでいることが、硬化速度と安定性のバランス、および施工性の点から好ましく、二酸化ケイ素を２５〜３６重量％と、酸化亜鉛を１２〜１３重量％と、酸化ナトリウムを６〜１１重量％と、酸化アルミニウムを５〜６重量％と、酸化ジルコニウムを４〜５重量％と、水と、を含むものであればより好ましい。 The obtained curable inorganic composition has 22 to 40% by weight of silicon dioxide (SiO 2 ), 10 to 15% by weight of zinc oxide (ZnO), and 3 to 15% of sodium oxide (Na 2 O) as components. Containing 3 wt%, aluminum oxide (Al 2 O 3 ) 3 to 10 wt%, zirconium oxide (ZrO 2 ) 2 to 8 wt%, and water. From the viewpoint of balance and workability, 25 to 36% by weight of silicon dioxide, 12 to 13% by weight of zinc oxide, 6 to 11% by weight of sodium oxide, 5 to 6% by weight of aluminum oxide, It is more preferable if it contains 4 to 5% by weight of zirconium oxide and water.

次に、本発明の実施例について説明する。   Next, examples of the present invention will be described.

本実施例では、水ガラスは市販のセメント用急結剤を、フライアッシュはＪＩＳ規格ＩＩ種のものを、酸化亜鉛はＪＩＳ規格１種のものを、ジルコンフラワーは９８％以上が粒子径４５μｍ以下のものを使用した。   In this example, water glass is a commercially available cement hardening agent, fly ash is JIS standard type II, zinc oxide is JIS standard type 1, zircon flour is 98% or more and particle size is 45 μm or less. I used one.

水ガラス１００ｇと、フライアッシュ３０ｇと、酸化亜鉛２０ｇと、ジルコンフラワー１０ｇと、少量の水とを容器に入れ、攪拌機を用いて室温のもとで約３分間攪拌した。攪拌後、組成物を密閉容器に移し、冷暗所で約１日間保管することで、硬化性無機組成物を製造した。   100 g of water glass, 30 g of fly ash, 20 g of zinc oxide, 10 g of zircon flour and a small amount of water were placed in a container and stirred for about 3 minutes at room temperature using a stirrer. After stirring, the composition was transferred to a sealed container and stored in a cool dark place for about 1 day to produce a curable inorganic composition.

得られた組成物は、灰色の粘性のある液体であり、各種材料の表面にヘラまたは刷毛で薄く塗り広げることができ、良好な施工性を有していることが確認された。また、得られた組成物は、比重が約１．８、ｐＨが約１２．２であり、成分および含有量は、ＳｉＯ２が２５〜３６重量％、ＺｎＯが１２〜１３重量％、Ｎａ２Ｏが６〜１１重量％、Ａｌ２Ｏ３が５〜６重量％、ＺｒＯ２が４〜５重量％であった。 The obtained composition was a gray viscous liquid, and could be spread thinly on the surface of various materials with a spatula or a brush, and it was confirmed that the composition had good workability. Further, the obtained composition has a specific gravity of about 1.8 and a pH of about 12.2, and the components and contents thereof are 25 to 36% by weight of SiO 2 , 12 to 13% by weight of ZnO, Na 2 O was 6 to 11% by weight, Al 2 O 3 was 5 to 6% by weight, and ZrO 2 was 4 to 5% by weight.

得られた組成物を、接着剤として用いた場合の接着強度をＪＩＳ Ｋ６８４９、Ｋ６８５０、Ｋ６８５７に基づいて試験したところ、図１に示す結果となった。同図に示されるように、常温で７２時間の乾燥後に十分な接着強度が得られ、高温下でも接着強度が極端に低下することはなかった。また、１時間の焼成によって十分な耐水性を有することが確認された。   When the obtained composition was used as an adhesive and tested for adhesive strength based on JIS K6849, K6850, K6857, the results shown in FIG. 1 were obtained. As shown in the figure, sufficient adhesive strength was obtained after drying for 72 hours at room temperature, and the adhesive strength did not extremely decrease even at high temperatures. Moreover, it was confirmed that it has sufficient water resistance by baking for 1 hour.

また、得られた組成物を接着剤として、木製の合板にビニル製の壁紙を貼付し、壁紙をガスバーナーで２分間連続して加熱（約８００℃）したところ、壁紙の加熱部分が炭化するのみで合板に変化はなかった。また、３分間連続してガスバーナーで加熱した場合も、壁紙および合板の加熱部分が炭化するのみで、合板が延焼することはなかった。これは、本実施例の硬化性無機組成物が加熱によりガラス化して発泡し、壁紙と合板の間に断熱性の不燃層を形成することにより、合板の延焼を防止するからである。すなわち、本実施例の硬化性無機組成物を合板や壁紙の接着剤として使用することにより、これらの建材に耐火性を持たせることができた。   In addition, when the obtained composition is used as an adhesive and vinyl wallpaper is attached to a wooden plywood and the wallpaper is continuously heated with a gas burner for 2 minutes (about 800 ° C.), the heated portion of the wallpaper is carbonized. There was no change in the plywood alone. Moreover, when it heated with the gas burner continuously for 3 minutes, only the heating part of wallpaper and the plywood carbonized, and the plywood did not spread. This is because the curable inorganic composition of the present example is vitrified and foamed by heating to form a heat-insulating incombustible layer between the wallpaper and the plywood, thereby preventing the plywood from spreading. That is, by using the curable inorganic composition of this example as an adhesive for plywood and wallpaper, it was possible to impart fire resistance to these building materials.

以上説明したように、本発明の硬化性無機組成物は、フライアッシュを使用することによって、品質や機能を劣化させることなく従来の無機系接着剤よりも安価に製造することができる。このため、建築の分野のように、従来コスト面から無機系接着剤があまり使われていなかった分野においても、耐熱性、耐火性に優れた接着剤として使用することができる。   As described above, by using fly ash, the curable inorganic composition of the present invention can be produced at a lower cost than conventional inorganic adhesives without deteriorating quality and function. For this reason, it can be used as an adhesive excellent in heat resistance and fire resistance even in a field where inorganic adhesives have not been used so much in terms of cost as in the field of construction.

また、各成分を適宜の割合で混合することによって、硬化速度を高めると共に良好な施工性を備えているため、接着剤以外にも、コーティング剤、塗料、充填剤等として幅広く使用することができる。さらに、保管時の安定性も備えることができるため、冷暗所に保管することで長期保存が可能となっている。   In addition, by mixing each component at an appropriate ratio, the curing rate is increased and good workability is provided, so that it can be widely used as a coating agent, paint, filler, etc. in addition to the adhesive. . Furthermore, since stability at the time of storage can be provided, long-term storage is possible by storing in a cool and dark place.

なお、本発明の硬化性無機組成物は、５〜１０℃の温度で冷蔵保存することにより、さらなる長期保管が可能である。   The curable inorganic composition of the present invention can be stored for a longer period of time by refrigerated storage at a temperature of 5 to 10 ° C.

また、本発明の硬化性無機組成物は、加熱された場合にガラス化して発泡し、断熱性の不燃層を形成するため、各種建材や構造材等に接着剤またはコーティング剤として塗布することにより、これらの部材の耐火性を高め、火災時の延焼を食い止めることができる。   In addition, the curable inorganic composition of the present invention vitrifies and foams when heated, and forms a heat-insulating incombustible layer. Therefore, it is applied to various building materials and structural materials as an adhesive or coating agent. The fire resistance of these members can be improved and the spread of fire during a fire can be prevented.

また、本発明の硬化性無機組成物を、成形物の結合材として使用することにより、耐火性に優れる耐火ボードを製造することができる。   Moreover, the fire-resistant board excellent in fire resistance can be manufactured by using the curable inorganic composition of this invention as a binder of a molded object.

なお、本発明に係る硬化性無機組成物は、上記した実施の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。   In addition, the curable inorganic composition according to the present invention is not limited to the above-described embodiment, and various changes can be made without departing from the scope of the present invention.

本発明に係る硬化性無機組成物は、建築の分野以外にも、耐熱性、耐火性を要求される接着剤、塗料、コーティング剤または充填剤等の分野において利用することができる。   The curable inorganic composition according to the present invention can be used in fields such as adhesives, paints, coating agents or fillers that require heat resistance and fire resistance, in addition to the field of architecture.

Claims (4)

水ガラスを１００重量部に対し、フライアッシュを２５〜３５重量部と、金属酸化物と、を予め混合してなることを特徴とする、硬化性無機組成物。   A curable inorganic composition obtained by previously mixing 25 to 35 parts by weight of fly ash and a metal oxide with respect to 100 parts by weight of water glass. 前記金属酸化物として酸化亜鉛を、水ガラス１００重量部に対して１５〜２５重量部を予め混合し、
さらにジルコンフラワーを、水ガラス１００重量部に対して５〜１５重量部を予め混合してなることを特徴とする、
請求項１に記載の硬化性無機組成物。 Zinc oxide as the metal oxide, 15 to 25 parts by weight in advance with respect to 100 parts by weight of water glass,
Further, the zircon flower is characterized by being previously mixed with 5 to 15 parts by weight with respect to 100 parts by weight of water glass.
The curable inorganic composition according to claim 1. 少なくとも前記水ガラスと、前記フライアッシュと、前記酸化亜鉛と、前記ジルコンフラワーと、を混合した結果、
二酸化ケイ素を２２〜４０重量％と、酸化亜鉛を１０〜１５重量％と、酸化ナトリウムを３〜１５重量％と、酸化アルミニウムを３〜１０重量％と、酸化ジルコニウムを２〜８重量％と、水と、を含むことを特徴とする、
請求項２に記載の硬化性無機組成物。 As a result of mixing at least the water glass, the fly ash, the zinc oxide, and the zircon flour,
22-40 wt% silicon dioxide, 10-15 wt% zinc oxide, 3-15 wt% sodium oxide, 3-10 wt% aluminum oxide, 2-8 wt% zirconium oxide, Including water,
The curable inorganic composition according to claim 2. 前記フライアッシュ、前記金属酸化物、および前記ジルコンフラワーは、それぞれ４５μｍ以下の粒子径のものが含まれることを特徴とする、
請求項２または３に記載の硬化性無機組成物。 The fly ash, the metal oxide, and the zircon flour each have a particle size of 45 μm or less,
The curable inorganic composition according to claim 2 or 3.
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